Solid-liquid reaction processes



1952 R. STANTON 2,615,906

SOLID-LIQUID/KEACTION PROCESSES Filed May 22, 1948 s Sheets-Sheet 1FIGJ.

INVENTOR. ROBERT STANTON BY v a ay-W #w 77%.

H/5 ATTORNEYS.

o 2 w M T 5 e c 1 h U Cu. w Y I 5 E 2 t m mm N u TO 2 h NT 0 s D mN "H aUT R NT r A L N 0 IS 5 s +m T E I E 5 A U T H S s C .R D R m Z M w E cVAR E E B R R P W N 0 Y m n B C m m 2 m s R M a m G E Q. U DA 6 m 23$ Ln, .r u o s M wA T U N LC DA 2 9 M ua 5 1 R 0A 9 SE 1 2 R 2 cm v. 2 m Id A d e 1 0 h Oct 28, 1952 R srr fl ofl -2,615,906

SOLID-LIQUID REACTION PROCESSES Fife d May 22, 1948 "3 Shee ts-Sheet aIN VEN TOR.

ROBERT STANTON H/S A T TORf/EYS Patented Oct. 28, 1952 UNITED STATESPATENT OFFICE SOLID-LIQUID REACTION PROCESSES Robert Stanton, Denver,Colo; Application Ma za 1948, Serial No. 28,613

11 Claims. (01.260-437) This invention relates to reaction processesinvolving a reactant in the form or a porous, frangible solid and areactant in the form of a liquid, more particularly to such processeswherein both the solid reactant and the liquid reactant are. broughttogether continuously, and it specifically relates to such processeswherein a solid reactant is saturated with a fluid reactant orpropellant under elevated pressure and introduced into the reaction zonewith abrupt or sudden pressure reduction which produces an appreciabledisruptive effect on the solid particles; the reaction is conductedcontinuously under high speed agitation induced by fluid propulsionacting upon the solid reactant particles to impart high speed theretowhile the movement of the reactant particles is regulated so that thehigh speed solid particles undergo high energy collisions.

Many usual processes of reacting a solid with a fluid reactant involvelarge reaction vessels, relatively slow and difficultly regulatedreaction procedure, and relatively large reaction mixtures. In somecases, health hazards such as explosions or the escape of toxic fumesarepresent.

In accordance with the invention, it has been found that such processescan be conducted in a rapid and relatively safe, readily regulatedmanner, with improved yields. Small reaction mixtures are suitable. Thenew processes may be conducted in a fully continuous manner and give ahighly desirable product. Theobjects achieved in accordance with theinvention include the provision of a process whereby thereaction of aporousrfrangible, solid reactant and a fluid reactant may be conductedin a continuous manner in a relatively small reaction zone; provisionera process for the preparation of 'alkylated lead by the reaction of alead' aikali alloy with alkyl halide in a continuous manner whereinrelatively small proportions of both reactants are involved at any onetime; the provision of a process for the preparation of tetraethyl leadby the reaction of coarsely divided lead-sodium alloy with ethylchloride in a continuous manner wherein relatively small proportions ofthe reactants are involved at any one time and wherein the particle sizeof the alloy is reduced as the reaction proceeds; and other objectswhich will be apparent as details and embodiments of the invention areset forth herematter.

In accordance with the invention, a reactant in the form of a coarselydivided, porous, frangible solid mixed with another reactant or'apropellant which is in the form of a fluid under elevated pressure, thenthe pressure is reduced abruptly and the reactants are mixed underhighspeed agitation induced by fluid propulsion, and the movement or thereactants is regulated so that the solid particles undergo high energycollisions; all under reaction temperature and pressure conditions. I

In an embodiment of the invention, the ream tion mass is shock expandedanddirectly subjected to rapid movement through acurved path; and theinfluence of the centrifugal force will cause the larger solid particlesto travel near the outer periphery of the curved path, and the smalleror lighter particles, to remain near the inner periphery of the curvedpath. This iacilitates the chemical reaction, and there will also be areduction in size of the larger particles associated with the highenergy collisions in the system. The reaction process takes placerapidlyand the fin'al reaction products and residue will be in a finely dividedstate near'the inner periphery of the curved path. v

A substantially completely reacted and more finely divided portion ofthe reaction mixture is removed from the inner periphery and then prooessed to recover reaction products, unconsumed reactants and by-productsor residues. I

The process may be conducted in a fully continuous manner, in apartially continuous or intermittent manner, or in a batch type process.The fully continuous process is preferred for commercial operation; 7 r

In order to facilitate a clear understanding of the invention, referencemaybe had to the accompany'ing drawings in which;

Figure 1 illustrates an arrangement of ia'n apparatu-s, partiallydiagrammatical and partially ins-ection', which may be employed forconducting the process of the invention, e. g., in the manufactureoftetraethyl lead.

Figure -2 represents a sketch of the process steps.

Figure 3 illustrates an alternative reaction chamber which may beemployed in connection with an arrangement of apparatus similar to thatin Figure 1.

Figures 4 and 5 illustrate details of injectors which may be used.

In Figure 1, a fluid propulsion reaction cham-,

of an endless conduit of uniform circular cross section.

A vertically disposed conical feed hopper I, which is closed at the topby the removable cover 2, communicates at its lower end with theconstant volume feed mechanism 3, which in turn communicates with thethroat portion of the downwardly inclined injector (Venturi) feed tube4. This feed tube is arranged to saturate the solid reactant with liquidreactant or propellant under elevated pressure and to abruptly reducethe pressure on the saturated solid reactant and discharge itsubstantially tangentially into the lower curved portion of the chamber5.

The chamber is provided with a plurality of substantially tangentiallydisposed high velocity fluid jets l, which are in communication with thefluid reactant supply tank I4 through pump I6, heater I1, and chamberI8. Tank I4 is equipped with a feed line I5.

An exhaust line 8 communicates with the chamber 5 at the inner peripheryand near the point where the upper semi-circular member 5A joins withthe vertical descending member 5D, thereof. The other end of the exhaustpipe 8 communicates substantially tangentially with the side of the lowvelocity cyclone separator 9. This separator is provided with an annulararrangement of downwardly directed spray nozzles I0,

positioned above the point of communication of a the exhaust line 8. Thetop of the cyclone separator is equipped with a partial condenser I2,and also communicates serially with the final condenser I3, which finalcondenser communicates with the fluid reactant feed tank I4.

, The lower end of the cyclone separator 9 communicates with a closedchamber II which is equipped with a strainer [9. The strainer I9communicates with the stripping column (which may be of the multipletray, or packed tower type). The column 210 communicates at its lowerend with the reboiler 2i. The reboiler 2| is equipped with a productremoval seal pipe 22.

The chamber II communicates with an upwardly inclined helicalribbon-type conveyor 25, which conveyor in turn communicates with astorage vessel 26. The conveyor is equipped with an annular heatingjacket 21 at the upper end thereof. with a vapor line 28, at a pointbelow the heating jacket 27, and it also communicates with a backwashline 30, at a point below the vapor line 28.

A solvent supply tank 24, which is equipped with a feed inlet (notshown), communicates through pump 29 with line 30. Line 39 alsocommunicates with the annular spray nozzles I0 through line 31. Tank 24also communicates with the upper part of the stripping column 20 throughline 32. The upper part of stripping column 20 communicates withcondenser 23 through line 28, and this condenser in turn communicateswith tank 25.

Figure 2 schematically illustrates the process. A fluid reactant and asolid reactant are brought Conveyor 25 also communicates h together inthe reactor, under reaction temperature and pressure conditions, withhigh speed fluid propulsion agitation. The solid reactant is saturatedwith fluid reactant 0r propellant under pressure and injected into thereactor with abrupt reduction in pressure, with accompanying disruptionof solid reactant particles. Reaction, attrition of solid particles andclassification of solid particles occur in the reactor. A substantiallycompletely reacted and finely divided part of 4 the reaction mixture ispassed from the reactor to a separator wherein the desired product isseparated. In addition, unconsumed fluid reactant may be separatelyrecovered, and unconsumed solid reactant collected as or in a residue.

Figure 3 illustrates an alternative type of reaction chamber. Asubstantially cylindrical chamber 43 communicates with solid reactantfeed hopper 40 (which is equipped with a cover, not shown) through theVenturi feed line 41 (arranged as discussed above for Figure 1). TheVenturi line also communicates with fluid line 42. Fluid jets 44communicate with chamber 43 at the outer circumference thereof, and aredirected tangentially to a circle of somewhat smaller radius than theouter radius of the chamber 43. The jets M and line 42 communicate withfluid jet lines Q5 and 46. The central portion of chamber 43communicates with chamber 48 and line 50. Chamber 48 is provided with aflange 41 which protrudes above the lower surface of chamber 43. Line 50is of smaller diameter than chamber 48, and the lower end of line 50 isset somewhat below the flange 41. Line 50 may be connected with a seriesof condensers at the upper end thereof, 5!. Chamber 48 may be connectedwith chamber I I of Figure 1 through throat 49.

Figure 4 illustrates-certain details of the injector l; I0! is ahigh-velocity nozzle for introducing fiuid at elevated pressure, I02 isa plenum chamber wherein a negative or reduced pressure is produced, I03is an inlet port for the introduction of a coarsely divided, porous,solid reactant, for instance by gravity feed from a supply source, I04is a convergent nozzle and throat portion, I05 is a saturating tubeportion, and I05 is an expansion tube portion.

Figure 5 shows an alternative form of an injector 4A, provided withvalve means for varying the degree of back-pressure maintained withinthe saturating tube portion. In this injector, I01 is a valve stem setin a stufling box I08, I09 is an axial-flow type valve closure, and I I0is a curved expansion tube portion. The distance of the valve closurefrom the seat or tube may be adjusted by means of screw threads or thelike (not shown).

If ethyl chloride vapor, applied at a pressure of 109 pounds per squareinch gauge, is passed through the injector, any pressure within therange of 0 up to 57 pounds per square inch gauge (at which point thereis a sharp change to backflow) may be maintained in the saturating tubeportion. The saturating tube portion may be constructed so that itscross-sectional area is uniform throughout its length, or it may bevaried, e. sli htly divergent toward the exit end; however, thecross-sectional area at any point thereof should not exceed the maximumcross-sectional area of the throat section. The throat portion ispreferably constructed with a 30 taper. It is preferred to maintain avacuum of at least about 10" Hg in the plenum chamber; however, this maybe varied depending upon the material handled.

Other types of curved path reaction chambers in which turbulent flow oragitation and classification may occur are suitable. The cross sectionneed not be tubular or cylindrical. Spiral, helical, reversed curve,annular, multistage, and the like shaped reaction vessels may beemployed. Combinations of tubular and vortex type chambers may be used.

If desired, fluid propulsion jets may be positioned at the outer part ornearer the inner part oi'sthe reaction chamber (cross section). seas: tincrease, deoreaseor otherwise modify turbulent flowin the chamber, e;.g., to. favor ormodify double inverse helical, flow, spiral iflow;transverse eddy currents; or thelilre therein.

In: one. embodiment, the, process, of the inventionmay be applied tothe. manufacture of tetra.- ethyl lead bythe reaction of lead' sodiumalloy and. ethyl chloride. Tetraethyl lead is'of great commercialimportance and itis consumed in large quantitiesv as an. ingredient, in;gasoline and the like internal, combustionrxengine fuels.

Various..methods have.v been: proposed heretofore for the manufactureoitetraethyl lead, e. g;, from'lead-sodium. alloy and ethyl chloride. Onetype involves charginga batch. of the (about 9.0% lead-% sodium) alloyinto. a reaction vessel and treating this: with: a batchor a continuousor intermittent stream of ethyl chloride. The reaction vessel may be inthe form of anautoclave equipped with a rotary stirrer, or arotatingball-mill, or similar batch type apparatus.

These'priorprocessos. are subject to many drawbacks. They involve longreaction periods and leaye'much. tobe desired as to yields- The alloyparticles'and the sodium chloride by-products of the reaction tend to.agglomeratc into larger lumpsand thusa substantial amount of the alloyistshiel'ded from. contact With the ethyl chloride reactants- Inaddition, the agglomerated mass retains a substantial amount of thetetraethyl leadproduct, and the recovery of the product therefrom istedious and wasteful.

There is considerable hazard involved in large batch operationscontaining a large charge of the alloy. The reaction may occur withexplosive violence. If moisture should happen to. come in contact withthe alloy, an explosion may occur. Where the process is conducted underpressure, there isconsiderable health hazard-from any of the highlytoxic tetraethyl lead vapors which might escape from the various valves,stufiing boxes and mechanical closures involved in batch type reactionvessels.

In accordance withthe invention, it has been found that the abovedrawbacks may be overcome and the tetraethyl lead produced in acommercially more advantageous manner.

A preparation of tetraethyl lead is given as an illustrative example ofan application of the invention. The reactant in solid form is porous,frangible alloy consisting of about 12.5% by weight of sodium and about87.5% by weight of lead..- This alloy may be conveniently preformed intosubstantially spherical shape, i. e., shot; in a conventional shottower. Alternatively it may be crushed or otherwise brought to'a coarsegrained size, preferably to pass through a 4 mesh (U. S. Sieve Series)test sieve. It is desirable to coat the alloy with kerosene or like oilymaterial so that it may be handled and transported more safely.

The hopper I is charged with the 4 mesh alloy, and the cover ZiS-put inplace. The fluid supply tank [4 is filled with ethyl chloride.Ethyl'chloride is maintained in the chamber 48: at a pressure ofabout'lOO pounds per square inch gauge and a temperature of about 180 F.The alloy is fed'into the reaction chamber 5 by means of the'feedermechanism 3 and the injector 6' (including the ethyl chloride jet fromline 5). Ethyl chlorideis also injected through jets 7.

Both the. amount of the ethyl chloride and'that of the lead used are inexcess of the stoichiometric requirements... Ereierably, the amount ofethyl chloride. is.. chosen. so. as: to.v imnartamaverae linear velocityor; aboutrlo; to. lilllieet. per second withinv the reaction, chamber,i..e., turbulent flow with transverse eddy currents. This. causesviesorous agitation therein, and associatedwith the highv energycollisions of the solid particles, rapid chemical erosion or attrition,or both, of the solid particles;. and also. a classification orseparation of thesubstantially completely reacted-and finely dividedmaterial from the coarser and less completely reacted material. Thepressure at the jets in the reaction chamber is high, relative to thepressure in the cyclone separator 9-.

The reaction temperature is preferably-main;- taincd at about to F.Reaction ofth'e ethyl chloride and the alloy occurs rapidly at theeffective contact surface. The propellant fluid is introduced throughjets 'i tangentially in the region Where the reactants are subjectedtothe highest compression, which compression is asso ciatedwith thecentrifugal force resulting from the curved path movement of the rapidlytraveling particles. The high compression is believed to intensify thereaction, and the turbulent flow movement imparted to the particles oithe fluid propellant which is tangentially introduced from the outerperiphery of this region insures that the reacting surface is maintainedin most reactive form by removal of any shielding coating and by themechanical stresses of the alloy particles associated with the highenergy collisio'nsin the reaction chamber and chemical erosion.Thebyproduct sodium chloride does not lump up or occlude unreacted alloyor finished reaction prod not, and it is maintained in a finely dividedState. The alloy particles may travel around the reaction chamber one ormore times in being reduced to a substantially completely reacted andfinely divided form.

A substantially completed reacted and finely divided portionof thereaction mixture travels near the inner periphery of the chamber 5,, andis withdrawn through exhaust line 8'. This withdrawn portion is thenprocessed to recovertetra: ethyl lead, unconsumed ethyl chloride, and. aresidue-which may contain recoverable lead. In one embodiment, theWithdrawn reaction mixture is passed to the low pressure cycloneseparator 9 and sprayed with acetone (from tank 24 through the spraynozzles in), The ethyl "chloride vapor undergoes a scrubbing due to theefiIect of the partial condenser l2, and then. passes upward to thecondenser l3, Where it is, con,- densed and returned to the ethylchloride tank l4. Additional make-up ethyl chloride maybe introducedthrough line I5, if necessary.

The acetone solution of tetraethyl lead plus the solid residue passes tochamber II. The acetone solution, removed therefrom through strainer I9,passes to the stripping column 20'. The acetone is vaporized, and thevapor passes to condenser 23, is condensed, and then passes to acetonesolvent tank 24. Finished tetraethyl lead is removed through line 22.

The solid residue passes from chamber, II to the conveyor 25 wherein itis back-washed with acetone, supplied through line 30. is then heated ata temperature of about 200? F. to expel acetone vapors and impart afinal drying efiectto the spent alloy. The, acetone vapor passes up tothe condenser 23, is liquefied, and then passes to tank 24. The spentalloy passes to chamber 26; It may be removed and processed to recoverany lead therein, in accordance with knownproccdures;

7 The reaction chamber may be supplied with a temperature regulatingjacket, or set in a temperature regulating bath, in order to regulatethe temperature thereof. Where the ethyl chloride is present as a vaporin the reaction chamber, the expansion of the ethyl chloride leaving thejets is accompanied by a refrigerating efiect. This may be adjusted soas to control the temperature of the reaction system, i. e., absorb theheat evolved by the exothermic chemical reaction in the formation of thetetraethyl lead.

The acetone spray in the separator serves to strip tetraethyl lead fromthe vapors as well as to help settle the spent alloy particles andbyproduct, sodium chloride. The effect of the partial condenser 12 is tofurther strip tetraethyl lead from the vapors of ethyl chloride.

It has been found that the recovered and recirculated ethyl chloridetends to give a higher yield of tetraethyl lead, than does fresh ethyl Achloride. It is thought that some material carried over in the recoveredethyl chloride has a beneficial effect on the reaction.

The process may be carried out in apparatus which includes heat exchangedevices; e. g., to i use the heat contained in the ethyl chloride vaporto preheat fresh ethyl chloride liquid.

The reactant in fluid form may contain a diluent or solvent and shouldbe readily flowable in order that sufiicient propulsion may be obatained without giving unduly high pressures. If the reactant is in theform of a liquid, it is pref- .erable that the Viscosity thereof shouldnot be higher than that of an about S. A. E. 50 motor lubricating oil atordinary room temperatures. The reaction may be conducted with the fluidreactant in either the vapor phase or the liquid phase.

In an illustrative vapor phase operation, a Figure 1 type of apparatusis used with a reaction chamber of 1.45 sq. inch inner crosssectionalarea, 3 inch radius of curvature upper and lower bends, and 18 inchvertical connectors;

the saturating tube portion of the injector is of the same innercross-sectional area as the reaction chamber, and three 5 inch jets areused. The following are representative operation conditions:

Pressure at Injector Inlets Pressure at Reactor Outlet Total EthylChloride Charged. Rate-Ethyl Chloride Fecd Tetraethyl Lead Produced.Yield Based on Sodium Consumed. Ethyl Chloride Consumed. 33 lbs 5.5 lbs.Yield Efiiciency Based on 94% 91%.

Ethyl Chloride. Average Size of Alloy Feed... 4 mesh mesh. Average Sizeof Lead Residue.. 5 microns. microns. Velocity at Reactor Outlet. F P.S. 10 F. P. S.

1 Pounds per square inch gauge. 9 Feet per second average linear massvelocity.

It is indeed surprising that this reaction can be carried out so readilyin accordance with the 8 above-described procedure, and in suchunexpectedly high yields. In the case of a process of preparingtetraethyl lead from the lead-sodium alloy and ethyl chloride in aball-mill, the alloy tends to clinker up into lumps which containunreacted alloy particles and lay-product sodium chloride and alsoocclude some tetraethyl lead. There is also a tendency for a caking orcoating of the balls (to form lumps) in the mill, and this willsimilarly isolate the two reactants from each other and occlude thereaction product so as to make recovery thereof difiicult.

In the normal operation of the above-described process, there will be noappreciable health hazards from the escape of tetraethyl lead vapors.The high pressure part of the reaction system, wherein tetraethyl leadoccurs, is completely closed. If desired, the pumping units may becompletely submerged within the corresponding tanks, in order to avoidpossible leakage of liquid from any stufling boxes or rotary shaftseals. If desired, the condensing units and tanks may be set at asuitable height relative to the remainder of the apparatus, so that thestatic pressure of the liquid will be suflicient for movement of theliquid without the use of pumps.

Other proportions of lead to alkali may be used in the alloy, e. g.,containing more than about 12.5% sodium. The alloy may be made up fromone or more alkali metals, e. g., mixtures of alkali metals may be used.Other organic halides may be used, c. g., ethyl bromide, and othersolvents than acetone may be used; as the art will readily appreciate inview of the above descriptions. A higher boiling fraction of gasolinemay be used as a solvent; and the solvent solution of the tetraethyllead could be directly blended with gasoline to give a desired motorfuel.

If desired, known promoters or catalysts may be included in the reactionmixture. Ferric chloride or anhydrous aluminum chloride may be suspendedin an inert vehicle, such as a petroleum distillate, and introduced incontrolled amounts into the reaction chamber at a convenient point.

If desired, the ethyl chloride vaporizing and condensing apparatus maybe replaced by a mechanical apparatus for developing the requiredpressure. Alternatively, an inert gas such as nitrogen may be employedas the fluid propulsion agent. In this case, the amount of the organichalide would be about sufficient to complete the chemical reaction. Thefluid reactant could be introduced in one set of one or more jets; andthe fluid propulsion agent, e. g., nitrogen in another set of one ormore jets.

If desired, the above-described product separation and recovery systemmay be replaced by conventional quenching and steam distillationmethods. For instance, the mixture of tetraethyl lead and spent alloycan be discharged from the lower end of the cyclone separator 9 into achamber containing a plurality of steam jets and then to a secondcyclone separator, wherein the spent alloy particles are separated by agravity effect, while the steam and tetraethyl lead vapor are removed,condensed, and the two immiscible liquids separately removed from thecondensate.

Where the alternative reaction chamber of Figure 3 is employed, it ispreferred that the fluid reactant be present in the form of a vapor,with or without additional or diluent gas.

In another application of the process of the invention, porous, solid,coarse grained calcium carbide is reacted with nitrogen gas at atemperature of about 400 C., to prepare solid calcium cyanamide. Thereaction chamber may be made of a special alloy, e. g; 18% nickel, 8%chromium, molybdenum, and the rest iron. The react-ionis :readilycontrolled, and gives a good yield of a uniform product; The requirementof a water treatment to remove unreacted calcium carbide issubstantially eliminated or reduced.

Another application of the .invention is in the reaction of solid,porous, coarse grained calcium cyanamide with'wet:steamcontaining about/2% sulphuric acid (based on weightlof steam) 'at about 100? -C. toprepare solid urea- -a -nd a byproduct calcium compound. The reaction isrelatively smooth and readily controlled, and gives a desirably uniformproduct. The urea may-be recovered by leaching with 'wa-te-r andseparating from the residue mud, in accordance with known procedures.

Another application of the-process of the invent-ion ;is in the reactionof-solid, porous aluminawith solid carbon and nitrogen gas to preparesolid aluminum nitride and carbon monoxide. The nitride may be separatedfrom the gas, by e. g., by gravity method, and then hydrolyzed withwater to give ammonia and aluminum hydroxide, both of which aredesirable products. The process gives an even mixture of the alumina andthe carbon, and avoids the coating of the alumina particles by a layerof the nitride.

Goods yields are obtained.

Another application of the process of the invention is in the treatmentof solid, porous coke with steam containing about 2% of phosphoric acid(based on the weight of steam) at about 1100 F. to produce activecarbon. The product may be used as a gas adsorbent carbon or as a liquidtreatment carbon. The process avoids the very undesirable clinkerformation, and also avoids the necessity of pelletizing the coke.

Another application of the invention is in the treatment of solid,porous phosphate rock with sulphuric acid in the preparation ofphosphoric acid and a calcium sulphate by-product. The acid may beseparated from the mud in accordance with known procedures.

Another application of the invention is in the treatment ofconcentrated, porous ilmanite (or rutile) with concentrated sulphuricacid to prepare titanium sulphate. The latter may be separated from theby-products, diluted with water and boiled to precipitate titaniumdioxide, in accordance with known methods. The reaction is smooth andreadily controlled, and the tendency of the sludge to slow up thereaction is substantially removed.

Another application of the invention is in the reaction of solid,porous, coarse grained sulphur with chlorine gas at about 35-50 C. andatmospheric pressure to prepare sulphur monochloride. The reaction isvery rapid and smooth, and gives good yields of a better product thanprior art processes. The product is relatively free from unreactedsulphur.

Another application of the invention is in the reaction of coarsegrained, porous magnesium metal with liquid ethyl chloride to preparethe Grignard reagent. The reaction is relatively rapid and smooth andreadily controlled. If desired, ethyl other could be used to wash theGrignard from the unreacted magnesium metal.

Another application of the invention is in the treatment of a poroussolid carbohydrate with mixed acid (e, g., nitric and sulphuric acid) toprepare oxalic acid. The oxalic acid may be separated from the residueby filtration orgrayity separation, in accordance with known inethlods.Suitable carbohydrates are' sawd-ust, cot ton linters, starch or grain.

Another application of the invention is in the treatment of milo maizewith dilute ;aqueous hydrochloric acid at about atmospheric temperatureand pressure to divest the SQiJd coat and to hydrolyze the starch togive invert sugar. The sligar may 5W3??? 193 1)? l b gravity, ac ordancw t lmewn methods- This eliminates the diificuity encountered intreating such seeds in ajFuss mill (lumping and caking, etc.) and thefinal product iso' amedin one operation without the needof largedigesting tanks.

Another application ofthe invention is in the act o of o id p rou ca c ma bis wi h a r vap c ntainin an a i suc a yd o.- chloric or acetic, togive the vinyl ester .of the acid. The estermay' be separate'd,froinfdreby.- product by gravity means. The reaction proceeds at about 50 C. andis readily controlled. A good quality product is obtained.

Another application of the invention is in the treatment of solid,porous sodium phenate with carbon dioxide to produce sodium salicylate,at 150 C. and at elevated pressure. The reaction is fast and gives adesirable product in good yields.

In view of the foregoing disclosures, the art will appreciate that othermethods may be used to bring together the reactant in porous solid formwith the reactant in fluid form, with or without an added propellant, soas to achieve the benefits of initial flash disruption and high speedfluid propulsion, while the reaction is in progress, together withmaintaining the solid reactant in active contact with the fluidreactant; e. g., by a shearing or cleaning action to remove anyshielding coating, or by mechanical stress of the solid particles topresent highly reactive solid reactant surface; and classifying orseparating substantially competely reacted and finely divided materialfrom the reaction zone. In view of the foregoing disclosures, variationsand modifications of applications of the invention will be apparent tothose skilled in the art; and the invention contemplates all such othermethods, variations and modifications except as do not come within theappended claims.

I claim:

1. A process for the preparation of alkylated lead comprising mixingcoarsely divided lead alkali metal alloy and alkyl chloride underelevated pressure and then abruptly reducing the pressure and mixingsaid reactants under high speed agitation induced by fluid propulsionwhile the movement of the mixture is confined to a closed substantiallyvertical elliptical path under reaction temperature and pressureconditions, said path having a region of highest compression at thelower end thereof, said reactants being subjected to the greatestcentrifugal compression in the region of highest compression resultingfrom the tangential introduction of a fluid propellant from the outerperiphery of said path whereby the chemical reaction is intensified andfresh reactant surfaces are maintained, and separating alkylated leadproduct from unreacted alkyl chloride and from residue.

2. A process of claim 1 which is carried out in a continuous manner andwherein the alloy is in the form of about 4 mesh particles.

3. A process of claim 2 wherein the reaction mixture contains a catalystand the alkyl chloride reactant is in the form of a liquid.

4. A process of claim 3 wherein the alkyl chloride is ethyl chloride.

5. A process of claim 4 wherein the high speed agitation is induced byan inert gas propellant.

6. A process of claim 4 wherein the removed more finely divided portionof the reaction mixture is contacted with a solvent for tetraethyl lead,and a solution of tetraethyl lead in said solvent is separated fromunreacted ethyl chloride and from the residue.

7. A process of claim 2 wherein the alkyl chloride reactant is in theform of a vapor.

8. A process of claim 7 wherein the alkyl chloride is ethyl chloride.

9. A process of claim 8 wherein the removed more finely divided portionof the reaction mixture is contacted with a solvent for tetraethyl lead,and a solution of tetraethyl lead in said solvent is separated fromunreacted ethyl chloride and from the residue.

ROBERT STANTON.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,962,173 Calcott et al. June 17,1934 2,237,091 Stephanofi Apr. 1, 1941 2,310,806 Nourse Feb. 9, 19432,351,091 Bar June 13, 1944 2,385,508 Hammond Sept. 25, 1945 2,391,723

Mann Dec. 25, 1945

1. A PROCESS FOR THE PREPARATION OF ALKYLATED LEAD COMPRISING MIXINGCOARSELY DIVIDED LEAD ALKALI METAL ALLOY AND ALKYL CHLORIDE UNDERELEVATED PRESSURE AND THEN ABRUPTLY REDUCING THE PRESSURE AND MIXINGSAID REACTANTS UNDER HIGH SPEED AGITATION INDUCED BY FLUID PROPULSIONWHILE THE MOVEMENTS OF THE MIXTURE IS CONFINED TO A CLOSED SUBSTANTIALLYVERTICAL ELLIPTICAL PATH UNDER REACTION TEMPERATURE AND PRESSURECONDITIONS, SAID PATH HAVING A REGION OF HIGHEST COMPRESSION AT THELOWER END THEREOF, SAID REACANTS BEING SUBJECTED TO THE GREATESTCENTRIFUGAL COMPRESSION IN THE REGION OF HIGHEST COMPRESSION RESULTINGFROM THE TANGENTIAL INTRODUCTION OF A FLUID PROPELLANT FROM THE OUTERPERIPHERY OF SAID PATH WHEREBY THE CHEMICAL REACTION IS INTENSIFIED ANDFRESH REACTANT SURFACES ARE MAINTAINED, AND SEPARATING ALKYLATED LEADPRODUCT FROM UNREACTED ALKYL CHLORIDE AND FROM RESIDUE.